p-methylenedioxyphenyl propionitrile derivatives, process for producing same, intermediates used in said process and organoleptic uses of said derivatives and intermediates

ABSTRACT

Described are p-methylenedioxyphenyl propionitrile and propiohydroxylamine derivatives defined according to the generic structure: ##STR1## wherein Z 1  represents the moiety: ##STR2## and the moiety: ##STR3## and R 1  is hydrogen or methyl and also having the generic structure: ##STR4## wherein X is HSO 4   --  ; SO 4  ;  =  Cl --  ; Br --  ; PO 4 .sup.═ ; H 2  PO 4   --  ; and HPO 4   =  ; and the process of preparing these compounds.

This is a divisional of application Ser. No. 006,605, filed Jan. 21,1993, pending.

BACKGROUND OF THE INVENTION

Our invention relates to p-methylenedioxyphenyl propionitrile andpropiohydroxylamine derivatives defined according to the structures:##STR5## wherein R₁ is hydrogen or methyl;

Z₁ is one of the moieties: ##STR6## M is 1, 2 or 3; and X is one of theanions:

HSO₄ ⁻⁻ ;

SO₄ ⁼ ;

Cl⁻⁻ ;

Br⁻⁻ ;

PO₄.sup.═ ;

H₂ PO₄ ⁻⁻ ; and

HPO₄ ⁼.

Our invention also covers the genus of compounds having the structure:##STR7## as well as the genus of compounds having the structure:##STR8## as novel compounds. Our invention also covers the uses of thecompounds having the structures: ##STR9## for their organoleptic (e.g.,perfumery) properties.

There has been considerable work performed relating to substances whichcan be used to impart (modify, augment or enhance) fragrances to (or in)various consumable materials. These substances are used to diminish theuse of natural materials, some of which may be in short supply and toprovide more uniform properties in the finished product.

Long-lasting intense substantive sweet, anisic, ozoney, ylang, geranium,melony, basil, floral and muguet aromas with sweet, anisic, ylang andgeranium topnotes are highly desirable in several types of perfumecompositions, perfumed articles and colognes (e.g., piney fragrances).

The perfume uses of nitrile-containing derivatives which contain phenylmoieties are well known in the prior art. Thus, the compounds definedaccording to the structure: ##STR10## wherein R₁ and R₂ are the same ordifferent and each represents hydrogen or methyl are disclosed in U.S.Pat. No. 5,143,899 issued on Sep. 1, 1992 (title "Process For PreparingPhenyl Butyronitriles And Perfumery Use Of 2,2-Dimethyl-4-PhenylValeronitrile"). Other perfume uses of nitrile-containing derivativeswhich also contain phenyl moieites are shown in U.S. Pat. No. 4,837,351issued on Jun. 6, 1989 wherein it is indicated that the compound havingthe structure: ##STR11## has a powerful, fresh, fruity, floral odor noteaccompanied by a citrus, green topnote. Furthermore, U.S. Pat. No.3,325,369 discloses the use of cinnamonitrile as a material useful inaugmenting or enhancing the aroma of perfume compositions.

Other nitriles containing gem-dimethyl moieties "alpha" to the cyanidemoiety are disclosed in Blumenthal, et al, U.S. Pat. No. 3,168,550issued on Feb. 2, 1965.

Nothing in the prior art discloses the use in perfumery of thep-methylenedioxyphenyl propionitrile and propiohydroxylamine derivativesof our invention.

However, the compound having the structure: ##STR12## is disclosed as achemical intermediate in the article by Semmelhack and Bargar,J.Am.Chem. Soc. 1980, 102(26) at pages 7765-7774 (abstracted at ChemicalAbstracts Volume 94:3607e); (title "Photostimulated NucleophilicAromatic Substitution For Halides with Carbon Nucleophiles. Preparativeand Mechanistic Aspects").

Nothing in the prior art, however, discloses the perfumery uses of thep-methylenedioxyphenyl propionitrile and propiohydroxylamine derivativesof our invention and nothing shows the use of the intermediates of ourinvention in the processes of our invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GC spectrum for the reaction product of Example Icontaining the compound having the structure: ##STR13## (Conditions:SE-30 column programmed at 150°-220° C. at 8° C. per minute).

FIG. 2 is the NMR spectrum for the compound having the structure:##STR14## produced according to Example I.

FIG. 3 is the infra-red spectrum for the compound having the structure:##STR15## produced according to Example I.

FIG. 4 is the GC spectrum for the reaction product of Example IIcontaining the compound having the structure: ##STR16##

FIG. 5 is the NMR spectrum for the compound having the structure:##STR17## produced according to Example II.

FIG. 6 is the infra-red spectrum for the compound having the structure:##STR18## produced according to Example II.

FIG. 7 is the GC spectrum for the compound having the structure:##STR19## produced according to Example III (Conditions: SE-30 columnprogrammed at 150°-220° C. at 8° C. per minute).

FIG. 8 is the NMR spectrum for the compound having the structure:##STR20## produced according to Example III.

FIG. 9 is the infra-red spectrum for the compound having the structure:##STR21## produced according to Example III.

FIG. 10 is a temperature-composition diagram showing a solid and liquidphase boundary for mixtures of the compound having the structure:##STR22## with the compound having the structure: ##STR23##

FIG. 11 represents a cut-away side elevation view of apparatus used informing performed polymers which contain imbedded therein certainp-methylenedioxyphenyl propionitrile and propiohydroxylamine derivativesof our invention including those having the structures: ##STR24##

FIG. 12 is a front view of the apparatus of FIG. 11 looking in thedirection of the arrows.

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GC spectrum for the reaction product of Example I(Conditions: SE-30 column programmed at 150°-220° C. at 8° C. perminute) 0.5 hours after the beginning of the reaction. The peaksindicated by reference numerals 10 and 12 are the peaks for the compoundhaving the structure: ##STR25## The peak indicated by reference numeral14 is the peak for the solvent, acetone.

FIG. 4 is the GC spectrum for the reaction product of Example IIcontaining the compound having the structure: ##STR26## The peakindicated by reference numeral 40 is the peak for the compound havingthe structure: ##STR27## (Conditions: SE-30 column programmed at150°-220° C. at 8° C. per minute).

FIG. 7 is the GC spectrum for the reaction product of Example IIIcontaining the compound having the structure: ##STR28## The peakindicated by reference numeral 70 is the peak for the compound havingthe structure: ##STR29##

(Conditions: SE-30 column programmed at 150°-220° C. at 8° C. perminute).

FIG. 10 is a temperature versus composition graph showing liquid phaseversus solid phase for compositions containing the compounds having thestructure: ##STR30## (indicated by the letter "A") and the compoundhaving the structure: ##STR31## (indicated by the letter "B"). The graphis indicated by the reference numeral 100. The area indicated by thereference numeral 102 is the area for the liquid phase. The areaindicated by reference numeral 104 is the area for the solid phase. Thepoint indicated by reference numeral 106 is a eutectic point.

Referring to FIGS. 11 and 12, there is provided a process for formingscented polymer elements (wherein the polymer may be a thermoplasticpolymer such as a low density polyethylene or polypropylene orcopolymers of ethylene and vinyl acetate or mixtures of polymers andcopolymers such as copolymers of ethylene and vinyl acetate andpolyethylene) such as pellets useful in the formation of plasticparticles useful in fabricating certain articles whicy may be perfumed(and, further, which may be exposed to chlorine bleaches). This processcomprises heating the polymer or mixture of polymers to the meltingpoint of said polymer or mixture of polymers, e.g. 250° C. in the caseof low density polyethylene. The lower most portion of the container ismaintained at a slightly lower temperature and the material in thecontainer is taken off at such location for delivery through theconduit. Thus, referring to FIGS. 11 and 12, in particular, theapparatus used in producing such elements comprises a device for formingthe polymer containing the perfume, e.g., polyethylene orpolyethylene-polyvinyl acetate or mixtures of same or polypropylene,which comprises a vat or container 212 into which the polymer takenalone or in admixture with other copolymers and the perfuming substancewhich is at least one of the materials having the structures: ##STR32##of our invention and other compatible perfumes is placed. The containeris closed by means of an air-tight lid 228 and clamped to the containerby bolts 265. A stirrer 273 traverses the lid or cover 228 in anair-tight manner and is rotatable in a suitable manner. A surroundingcylinder 212A having heating coils which are supplied with electriccurrent through cable 214 from a rheostat or control 216 is operated tomaintain the temperature inside the container 212 such that the polymerin the container will be maintained in the molten or liquid state. Ithas been found advantageous to employ polymers at such a temperaturethat the viscosity will be in the range of 90-100 sayboldt seconds. Theheater 218 is operated to maintain the upper portion of the container212 within a temperature range of, for example, 220°-270° C. in the caseof low density polyethylene. The bottom portion of the container 212 isheated by means of heating coils 212A regulated through the control 220connected thereto through a connecting wire 222 to maintain the lowerportion of the container 212 within a temperature range of 220°-270° C.

Thus, the polymer or mixture of polymers added to the container 212 isheated from 10-12 hours, whereafter the perfume composition or perfumematerial which contains at least one of the compounds having thestructures: ##STR33## of our invention is quickly added to the melt.Generally, about 10-45 percent by weight of the resulting mixture of theperfumery substance is added to the polymer.

After the perfume material is added to the container 212, the mixture isstirred for a few minutes, for example, 5-15 minutes and maintainedwithin the temperature ranges indicated previously by the heating coil212A. The controls 216 and 220 are connected through cables 224 and 226to a suitable supply of electric current for supplying the power forheating purposes.

Thereafter the valve "V" is opened permitting the mass to flow outwardlythrough conduit 232 having a multiplicity of orifices 234 adjacent tothe lower side thereof. The outer end of the conduit 232 is closed sothat the liquid polymer in in itimate admixture with at least one of thecompounds having the structures: ##STR34## of our invention and one ormore other substances, will continuously drop through the orifices 234downwardly from the conduit 232. During this time, the temperature ofthe polymer intimately admixed with the perfumery substance in thecontainer 212 is accurately controlled so that a temperature in a rangeof from about 240°-250° C., for example, (in the case of low densitypolyethylene) will exist in the conduit 232. The regulation of thetemperature through the controls 216 and 220 is essential in order toinsure the temperature balance to provide for the continuous dripping ordropping of molten polymer intimately admixed with the perfume substancewhich is at least one of the compounds having the structures: ##STR35##of our invention through the orifices 234 at a rate which insure theformation of droplets 236 which will fall downwardly onto a movingconveyor belt 238 caused to run between conveyor wheels 240 and 242beneath the conduit 232.

When the droplets 236 fall onto the conveyor 238, they form pellets 244which harden almost instantaneously and fall off the end of the conveyor238 into a container 250 which is advantageously filled with water orsome other suitable cooling liquid to insure the rapid cooling of eachof the pellets 244. The pellets 244 are then collected from thecontainer 250 and utilized for the formation of functional products,e.g., garbage bags and the like.

THE INVENTION

The present invention provides p-methylenedioxyphenyl propionitrile andpropiohydroxylamine derivatives as well as the uses of a number of suchp-methylenedioxyphenyl propionitrile and propiohydroxylamine derivativeshaving the structures: ##STR36## in augmenting or enhancing or impartingaroma to or in perfume compositions, perfumed articles and colognes.

The p-methylenedioxyphenyl propionitrile and propiohydroxylaminederivatives of our invention are those defined according to the genericstructure: ##STR37## wherein R₁ is hydrogen or methyl and Z₁ is one ofthe moieties: ##STR38## and compounds defined according to the genericstructure: ##STR39## wherein M is an integer selected from the groupconsisting of 1, 2 or 3; and X is an anion which is one of the anions:##STR40##

The compounds having the structures: ##STR41## have uses in augmentingor enhancing the aroma of perfume compositions, colognes and perfumedarticles, including but not limited to perfumed polymers, cosmeticpowders, anionic, cationic, nonionic or switterionic detergents, fabricsoftener compositions, fabric softener articles including drier-addedfabric softener articles (e.g., BOUNCE® marketed by the Proctor & GambleCompany of Cincinnati, Ohio). Of particular significance in ourinvention are liquid mixtures of the compounds having the structures:##STR42## since these two materials are themselves crystalline solids.When admixed and heated, the two materials form a eutectic mixture at68° C. as shown by FIG. 10 described, supra.

Thus, the compounds having the structures: ##STR43## as well as variousmixtures thereof including the liquid mixtures of compounds having thestructures: ##STR44## including its eutectic mixture are capable ofimparting, augmenting or enhancing sweet, anisic, ozoney, ylang,geranium, melony, basil, floral and muguet aromas with sweet, anisic,ylang and geranium topnotes to perfume compositions, colognes andperfumed articles including soaps, bleaches, anionic, cationic, nonionicor zwitterionic detergents, fabric softener articles and other perfumedarticles.

The process of our invention involves first reacting the compound havingthe structure: ##STR45## with a hydroxylamine acid salt having theformula: ##STR46## wherein M is an integer selected from the groupconsisting of 1, 2 or 3 and X is defined, supra to form the novelcompounds defined according to the structure: ##STR47## for example, thebisulfate salt having the structure: ##STR48## The resulting saltdefined according to the structure: ##STR49## is then reacted with base,e.g., aqueous sodium hydroxide to form the hydroxylamine base definedaccording to the structure: ##STR50## This material is in an of itself aperfumery substance, particularly when admixed with the material havingthe structure: ##STR51## shown to be produced, infra.

The compound having the structure: ##STR52## may then be reacted withthe dehydrating agent, for example, cupric sulfate in combination withacetic anhydride to form the nitrile having the structure: ##STR53##Thus, the reaction sequence for the foregoing two reactions is asfollows: ##STR54##

The compound having the structure: ##STR55## thus formed can be used asis for its perfumery properties or it can be further alkylated usingmethyl iodide in the presence of a lithium diisopropyl amide catalysthaving the structure: ##STR56## according to the reaction: ##STR57##

The resultant product is then crystallized and purified in accordancewith standard practices for purification of a material which is solid atambient conditions.

With reference to the reaction, to wit: ##STR58## the reaction takesplace in aqueous media at a temperature of between about 5° C. and about10° C.

With reference to the reaction: ##STR59## the reaction takes place inaqueous media using, for example, aqueous sodium hydroxide over a periodof time of between about one and about three hours at a temperature ofbetween about 35° C. and about 50° C. At the end of the reaction, theresulting product is crystallized and purified by standard purificationtechniques of materials which are solid at ambient conditions.

The reaction, to wit: ##STR60## takes place at a temperature of betweenabout 100° and 110° C. for a period of time of from about one up toabout ten hours (preferably between about three and about seven hours).The dehydration reagent preferred in this reaction is a mixture ofacetic anhydride and cupric sulfate. At the end of the reaction, thereaction product is fractionally distilled after appropriate "workup"and the fractional distillation of the compound having the structure:##STR61## is at a vapor temperature of 130° C. and a vacuum of 1.55mm/Hg.

The methylation reaction, to wit: ##STR62## using methyl iodide takesplace using preferably a lithium diisopropylamide catalyst having thestructure: ##STR63## using preferably a solvent which is composed oftetrahydrofuran, ethyl benzene and heptane. The reaction takes place ata temperature in the range of from about 40° up to about 70° C. over aperiod of about three hours. At the end of the reaction, the reactionproduct having the structure: ##STR64## is crystallized and purifiedusing standard purification procedures for materials which arecrystalline at ambient conditions.

Perfumery use of the compound having the structure: ##STR65## is eitherin solution, e.g., in diethyl phthalate solution or in admixture withother materials whereby a eutectic composition is formed, for example,in admixture with the compound having the structure: ##STR66## The highmelting eutectic (68° C.) for the eutectic mixture of the compoundshaving the structures: ##STR67## causes such mixture to be useful inbath oils where the higher temperature will bring out the intenseanisic, floral, muguet and sweet aroma of such mixture.

The following table sets forth the perfumery properties of the variouscompositions of matter so useful in perfumery of our invention:

                  TABLE I                                                         ______________________________________                                        Description of Composition                                                                         Perfumery Properties                                     ______________________________________                                        Compound having      A sweet, anisic, ozoney,                                 the structure:       ylang, geranium and                                       ##STR68##           melony aroma with sweet, anisic, ylang and geranium                           topnotes.                                                (50% solution in                                                              diethyl phthalate)                                                            prepared according                                                            to Example III.                                                               Compound having      A sweet, basil aroma.                                    the structure:                                                                 ##STR69##                                                                    prepared according                                                            to Example II.                                                                75:25 (Weight:weight)                                                                              An intense anisic, floral,                               mixture of compounds muguet and sweet aroma                                   having the structure:                                                                              profile (at 68° C.).                               ##STR70##                                                                    and                                                                            ##STR71##                                                                    ______________________________________                                    

The compounds having the structures: ##STR72## as well as mixturesthereof of our invention and one or more auxiliary perfume ingredients,including, for example, hydrocarbons, alcohols, ketones, aldehydes,nitriles (other than the nitriles of our invention), esters, lactones,ethers, hydrocarbons, synthetic essential oils and natural essentialoils may be admixed so that the combined odors of the individualcomponents produce a pleasant and desired fragrance particularly andpreferably in the "pine fragrance" area. Such perfume compositionsusually contain (a) the main note or the "bouquet" or foundation stoneof the composition; (b) modifiers which round off and accompany the mainnote; (c) fixatives which include odorous substances which lend aparticular note to the perfume throughout all stages of evaporation andsubstances which retard evaporation; and (d) topnotes which are usuallylow boiling, fresh smelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however, theoverall sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, at least oneof the compounds having the structures: ##STR73## or mixtures thereof ofour invention can be used to alter, modify or enhance the aromacharacteristics of a perfume composition, for example, by utilizing ormoderating the olfactory reaction contributed by another ingredient inthe composition.

The amount of at least one of the compounds having the structures:##STR74## or mixtures thereof of our invention which will be effectivein perfume compositions as well as in perfumed articles and colognesdepends upon many factors, including the other ingredients, theiramounts and the effects which are desired.

It has been found that perfume compositions containing as little as0.05% of at least one of the compounds having the structures: ##STR75##or mixtures thereof of our invention can be used to impart sweet,anisic, ozoney, ylang, geranium, melony, basil, floral and muguet aromaswith sweet, anisic, ylang and geranium topnotes to soaps, cosmetics,detergents (including anionic, cationic, nonionic or zwitterionic solidor liquid detergents) or other products. The amount employed can rangeup to 70% of the fragrance components and will depend uponconsiderations of cost, nature of the end product, the effects desiredon the finished product and the particular fragrance sought.

At least one of the compounds having the structures: ##STR76## ormixtures thereof are useful (taken alone or together with otheringredients in perfume compositions), in detergents and soaps, spaceodorants and deodorants, perfumes, colognes, toilet water, bathpreparations such as lacquers, brilliantines, pomades and shampoos;cosmetic preparations such as creams, deodorants, hand lotions and sunscreens; powders, such as talcs, dusting powders, face powders and thelike.

As little as 0.7% of at least one of the compounds havin the structures:##STR77## or mixtures thereof of our invention will suffice to impart anintense and substantive sweet, anisic, ozoney, ylang, geranium, melony,basil, floral and muguet aromas with sweet, anisic, ylang and geraniumtopnotes to pine perfume formulations. Generally, no more than 5% of atleast one of the compounds having the structures: ##STR78## or mixturesthereof of our invention based on the ultimate end product is requiredto be used "as is" or in the perfume composition.

Furthermore, as little as 0.25% of at least one of the compounds havingthe structures: ##STR79## or mixtures thereof of our invention willsuffice to impart such aroma to perfumed articles per se, whether in thepresence of other perfume materials or whether used by themselves. Thus,the range of use of at least one of the compounds having the structures:##STR80## or mixtures thereof of our invention in perfumed articles mayvary from about 0.25% up to about 5% by weight based on the total weightof the perfumed article.

In addition, the perfume composition or fragrance compositions of ourinvention can contain a vehicle, or carrier for at least one of thecompounds having the structures: ##STR81## or mixtures thereof of ourinvention. The vehicle can be a liquid such as a non-toxic alcohol,e.g., ethanol, a non-toxic glycol, e.g., propylene glycol or the like.The carrier can also be an absorbent solid, such as a gum (e.g., gumarabic), or components for encapsulating the composition as by means ofcoacervation (such as gelatin).

It will thus be apparent that at least one of the compounds having thestructures: ##STR82## or mixtures thereof of our invention can beutilized to alter, modify or enhance the aroma of perfume composition,colognes or perfumed articles.

Furthermore, a number of processes known in the art and set forth, forexample, in U.S. Pat. No. 5,143,899 issued on Sep. 1, 1992, thespecification for which is incorporated by reference herein may be usedin order to produce a thickened, highly viscous hypochlorite bleachingor sterilizing solution, whereby the desired aroma profiles are impartedto the articles treated with such hypochlorite solutions. Specifically,the disclosure set forth at columns 12, 13, 14, 15, 16, 17 and 18 ofsaid U.S. Pat. No. 5,143,899 is incorporated by reference herein.

The following Examples I, II and III serve to illustrate processes forpreparing the p-methylenedioxyphenyl propionitrile andpropiohydroxylamine derivatives of our invention.

Examples following Example III in general serve to illustrate theorganoleptic utilites of the compounds having the structures: ##STR83##or mixtures thereof of our invention.

In general, the following examples serve to illustrate specificembodiments of our invention. It will be understood that these examplesare illustrative and that the invention is to be considered restrictedthereto only as indicated in the appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I Preparation of Alpha-Methyl-3,4-(Methylene Dioxy)Hydrocinnamaldehyde Oxime Reactions ##STR84##

Into a 12 liter reaction vessel equipped with stirrer, thermometer,cooling coils and heating mantle as well as reflux condenser are placeda mixture of 2500 ml water and 1179 grams (7.14 moles) of hydroxylaminesulfate. The resulting mixture is stirred until homogeneous. Over aperiod of five minutes while maintaining the reaction mass at 7° C., thecompound having the structure: ##STR85## in an amount of 1600 grams (10moles) is added to the reaction mass. The reaction mass is stirred for aperiod of about five minutes. The compound having the structure:##STR86## is thus formed.

Over a period of two hours, 1314 grams of 50% aqueous sodium hydroxide(containing 657 grams of solid sodium hydroxide) is added to thereaction mass. The reaction mass exotherms to 42° C. and is maintainedat between 38 and 42° C. for a period of three hours (with stirring).

The reaction mass now exists in two phases; an aqueous phase and anorganic phase. Two liters of methylene dichloride is added to thereaction mass.

The organic phase is now separated from the aqueous phase and theorganic phase is washed with two 1000 ml portions of saturated sodiumchloride and then dried over anhydrous magnesium sulfate. The resultingproduct is filtered and then cooled and the product having thestructure: ##STR87## is isolated in the form of crystals (yield:1420grams). The structure of the resulting product is confirmed by NMR andIR analyses as set forth in the description of FIGS. 2 and 3, supra.

The resulting product when mixed in a 75:25 weight (weight:weight) ratiowith the compound having the structure: ##STR88## has an intense anisic,floral, muguet and sweet aroma profile. The resulting compound forms aeutectic mixture with the compound having the structure: ##STR89## at68° C. as shown in FIG. 10 described, supra. The liquid-solid phaseboundary of various mixtures of the compound having the structure:##STR90## and the compound having the structure: ##STR91## are set forthin FIG. 10 with the graph showing the boundary between the solid andliquid phases being indicated by reference numeral 100. The area showingthe solid phase is indicated by reference numeral 104 and the areashowing the liquid phase is indicated by reference numeral 102. Theeutectic point at 68° C. is indicated by reference numeral 106. The75:25 (weight:weight) mixture of the compound having the structure:##STR92## the compound having the structure: ##STR93## exists at 80° C.and it, too, has an intense anisic, floral, muguet and sweet aroma. Thismixture is particularly useful in bath oils used in hot baths where thearoma is particularly striking, intense and substantive. Thus, the usein hot bath oils is of particular interest for such mixtures.

EXAMPLE II Preparation of Alpha-Methyl-3,4-(Methylenedioxy)Hydrocinnamonitrile Reaction ##STR94##

Into a 5 liter reaction flask equipped with stirrer, thermometer, refluxcondenser and heating mantle are placed 963 grams (9.44 moles) of aceticanhydride and 6 grams of cupric sulfate. The resulting mixture withstirring is heated to 100° C. While maintaining the reaction mass at100° C., over a period of three hours, 1303 grams (6.29 moles) of thecompound having the structure: ##STR95## is added to the reaction mass.The reaction mass is then stirred for a period of six hours whilemaintaining the temperature thereof at 100° C.

The reaction mass is then quenched with 2 liters of water reducing thetemperature of the mixture to 30° C.

The reaction mass now exists in two phases; an organic phase and anaqueous phase. The aqueous phase is extracted with 300 ml toluene andthe toluene extract is combined with the organic phase. The resultingorganic phase is then washed with 1000 ml water followed by 500 ml of a10% aqueous sodium bicarbonate solution followed by 500 ml of asaturated sodium chloride solution.

The resulting product is then filtered through anhydrous magnesiumsulfate and distilled through a fractionation column yielding thefollowing fractions:

    ______________________________________                                                  Vapor        Liquid  Vacuum                                         Fraction  Temp.        Temp.   mm/Hg.                                         No.       (°C.) (°C.)                                                                          Pressure                                       ______________________________________                                        1         27/42        48/82   100/2.56                                       2         130          140     1.55                                           3         110          200      1.62.                                         ______________________________________                                    

Fraction 2 is the material which has the structure: ##STR96## Thiscompound has a sweet, basil aroma. The structure of the compound, towit: ##STR97## is confirmed by NMR and IR analyses as set forth in thedescription of FIGS. 5 and 6, supra.

EXAMPLE III Preparation of Alpha,Alpha-Dimethyl-3,4-(Methylenedioxy)Hydrocinnamonitrile Reaction ##STR98##

Into a 5 liter reaction flask equipped with cooling oils, thermometer,reflux condenser and heating mantle are placed 2.0 moles of lithiumdiisopropyl amide having the structure: ##STR99## in a solvent which isa mixture of tetrahydrofuran, ethyl benzene and heptane. The resultingmixture is cooled to 0° C. Over a period of one hour while maintainingthe temperature at between 0° and 5° C., 630 grams (3.2 moles) of thecompound having the structure: ##STR100## produced according to ExampleII is added to the reaction mass with stirring. The reaction mass iscooled to 0° C. and stirred for a period of 0.5 hours. At the end of the0.5 hour period, over a period of one hour, 691 grams (4.87 moles) ofmethyl iodide is added to the reaction mass. The reaction mass isstirred at 60° C. for a period of three hours; and then cooled to 35° C.The reaction mass is then quenched with 1 liter of 2 molar hydrochloricacid. The reaction mass is then admixed with 400 ml concentratedhydrochloric acid. The reaction mass now exists in two phases; anaqueous phase and an organic phase. The organic phase is washed with2000 ml water followed by 500 ml 10% aqueous sodium bicarbonate followedby 500 ml saturated sodium chloride solution. The reaction mass is thenfiltered through anhydrous magnesium sulfate and distilled to yield 285grams of product, through a fractionation column yielding the followingfractions:

    ______________________________________                                                    Vapor      Liquid     Vacuum                                      Fraction    Temp.      Temp.      mm/Hg.                                      No.         (°C.)                                                                             (°C.)                                                                             Pressure                                    ______________________________________                                        1           45/        112/       4.90/                                       2           147/130    152/200    3.56/9.08.                                  ______________________________________                                    

The resulting product crystallizes. The structure, to wit: ##STR101## isconfirmed via NMR and IR analyses as shown in FIGS. 8 and 9.

A 50% solution of the resulting product in diethyl phthalate has asweet, anisic, ozoney, ylang, geranium and melony aroma with sweet,anisic, ylang and geranium topnotes.

EXAMPLE IV

The following Chypre formulations are prepared:

    ______________________________________                                                           Parts by Weight                                            Ingredients          IV(A)   IV(B)   IV(C)                                    ______________________________________                                        Musk ambrette        40      40      40                                       Musk ketone          60      60      60                                       Coumarin             30      30      30                                       Oil of bergamot      150     150     150                                      Oil of lemon         100     100     100                                      Methyl ionone        50      50      50                                       Hexyl cinnamic aldehyde                                                                            100     100     100                                      Hydroxycitronellal   100     100     100                                      Oil of lavender      50      50      50                                       Texas cedarwood oil  85      85      85                                       Virginia cedarwood oil                                                                             30      30      30                                       Oil of sandalwood    40      40      40                                       (East Indies)                                                                 Eugenol              10      10      10                                       Benzyl acetate       30      30      30                                       alpha-Phenyl ethyl alcohol                                                                         40      40      40                                       beta-Phenyl ethyl alcohol                                                                          30      30      30                                       Oakmoss absolute     30      30      30                                       Vetiver oil Venezuela                                                                              25      25      25                                       The compound having  62       0       0                                       the structure:                                                                 ##STR102##                                                                   (50% in diethyl                                                               phthalate) prepared                                                           according to Example III.                                                     The compound having   0      62       0                                       the structure:                                                                 ##STR103##                                                                   prepared according                                                            to Example II.                                                                A 75:75 (weight:weight)                                                                             0       0      62                                       mixture of the compound                                                       having the structure:                                                          ##STR104##                                                                   and the compound                                                              having the structure:                                                          ##STR105##                                                                   ______________________________________                                    

The compound having the structure: ##STR106## (50% in diethyl phthlate)prepared according to Example III imparts to this Chypre formulationsweet, anisic, ozoney, ylang, geranium and melony undertones with sweet,anisic, ylang and geranium topnotes. Accordingly, the Chypre formulationof Example IV(A) can be described as "a Chypre aroma with sweet, anisic,ozoney, ylang, geranium and melony undertones and sweet, anisic, ylangand geranium topnotes".

The compound having the structure: ##STR107## prepared according toExample II imparts to this Chypre formulation intense and substantivesweet and basil undertones. Accordingly, the Chypre formulation ofExample IV(B) can be described as having "a Chypre aroma with sweet andbasil undertones".

The mixture of compounds having the structures: ##STR108## (75:25weight:weight) imparts to this Chypre formulation intense anisic,floral, muguet and sweet undertones. Accordingly, the perfumecomposition of Example IV(C) can be described as having "a Chypre aromawith intense anisic, floral, muguet and sweet undertones".

EXAMPLE V Preparation of Cosmetic Powder Compositions

Cosmetic powder compositions are prepared by mixing in a ball mill 100grams of talcum powder with 0.25 grams of each of the substances setforth in Table II below. Each of the cosmetic powder compositions has anexcellent aroma as described in Table II below:

                  TABLE II                                                        ______________________________________                                        Substance            Aroma Description                                        ______________________________________                                        The compound having  A sweet, anisic, ozoney,                                 the structure:       ylang, geranium and                                       ##STR109##          melony aroma with sweet, anisic, ylang and geranium                           topnotes.                                                (50% in diethyl                                                               phthalate) prepared                                                           according to Example III.                                                     The compound having  A sweet and basil                                        the structure:       aroma.                                                    ##STR110##                                                                   prepared according                                                            to Example II.                                                                75:25 (Weight:weight)                                                                              An intense anisic, floral,                               mixture of compounds muguet and sweet aroma                                   having the structures:                                                                             profile.                                                  ##STR111##                                                                   and                                                                            ##STR112##                                                                   Perfume composition  A Chypre aroma with                                      of Example IV(A).    sweet, anisic, ozoney,                                                        ylang, geranium and                                                           melony undertones and                                                         sweet, anisic, ylang and                                                      geranium topnotes.                                       Perfume composition  A Chypre aroma with                                      of Example IV(B).    sweet and basil                                                               undertones.                                              Perfume composition  A Chypre aroma with                                      of Example IV(C).    intense anisic, floral,                                                       muguet and sweet                                                              undertones.                                              ______________________________________                                    

EXAMPLE VI Perfumed Liquid Detergent

Concentrated liquid detergents (Lysine slat of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818 issued onApr. 6, 1976) with aroma nuances as set forth in Table II of Example Vare prepared containing 0.10%, 0.15%, 0.20%, 0.25%, 0.30% and 0.35% ofthe substance set forth in Table II of Example V. They are prepared byadding and homogeneously mixing the appropriate quantity of substanceset forth in Table II of Example V in the liquid detergent. Thedetergents all possess excellent aromas as set forth in Table II ofExample V, the intensity increasing with greater concentration ofsubstance set forth in Table II of Example V.

EXAMPLE VII Preparation of Colognes and Handkerchief Perfumes

Compositions as set forth in Table II of Example V are incorporated intocolognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% and5.0% in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions; andinto handkerchief perfumes at concentrations of 15%, 20%, 25% and 30%(in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions).Distinctive and definitive fragrances as set forth in Table II ofExample V are imparted to the colognes and to the handkerchief perfumesat all levels indicated.

EXAMPLE VIII Preparation of Soap Compositions

One hundred grams of soap chips [per sample] IVORY®, produced by theProcter & Gamble Company of Cincinnati, Ohio), are each mixed with onegram samples of substances as set forth in Table II of Example V untilhomogeneous compositions are obtained. In each of the cases, thehomogeneous compositions are heated under 8 atmospheres pressure at 180°C. for a period of three hours and the resulting liquids are placed intosoap molds. The resulting soap cakes, in cooling, manifest aromas as setforth in Table II of Example V.

EXAMPLE IX Preparation of Solid Detergent Compositions

Detergents are prepared using the following ingredients according toExample I of Canadian Patent No. 1,007,948:

    ______________________________________                                        "NEODOL ® 45-11      12                                                   (a C.sub.14 -C.sub.15 alcohol                                                 ethoxylated with 11 moles                                                     of ethylene oxide                                                             Sodium carbonate         55                                                   Sodium citrate           20                                                   Sodium sulfate, water    q.s.                                                 brighteners                                                                   ______________________________________                                    

This detergent is a phosphate-free detergent. Samples of 100 grams eachof this detergent are admixed with 0.10, 0.15, 0.20 and 0.25 grams ofeach of the substances as set forth in Table II of Example V. Each ofthe detergent samples has an excellent aroma as indicated in Table II ofExample V.

EXAMPLE X

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396, non-woven cloth substrates useful as drier-added fabricsoftening articles of manufacture are prepared wherein the substrate,the substrate coating and the outer coating and the perfuming materialare as follows:

1. a water "dissolvable" paper ("Dissolvo Paper");

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. an outer coating having the following formulation (m.p. about 150°F.):

57%--C₂₀₋₂₂ HAPS;

22%--isopropyl alcohol;

20%--antistatic agent;

1%--of one of the substances as set forth in Table II of Example V.

Fabric softening compositions prepared according to Example I at column15 of U.S. Pat. No. 3,632,396 having aroma characteristics as set forthin Table II of Example V, consist of a substrate coating having a weightof about 3 grams per 100 square inches of substrate; a first coating onthe substrate coating consisting of about 1.85 grams per 100 squareinches of substrate; and outer coating coated on the first coatingconsisting of about 1.4 grams per 100 square inches of substrate. One ofthe substances of Table II of Example V is admixed in each case with theouter coating mixture, thereby providing a total aromatized outercoating weight ratio to substrate of about 0.5:1 by weight of thesubstrate. The aroma characteristics are imparted in a pleasant mannerto the head space in a dryer on operation thereof in each case usingsaid drier-added fabric softener non-woven fabrics and these aromacharacteristics are described in Table II of Example V.

EXAMPLE XI Hair Spray Formulations

The following hair spray formulation is prepared by first dissolvingPVP/VA E-735 a copolymer manufactured by the GAF Corporation of 140 West51st Street, New York, N.Y., in 91.62 grams of 95% food grade ethanol,8.0 grams of the polymer is dissolved in the alcohol. The followingingredients are added to the PVP/VA alcoholic solution:

    ______________________________________                                        Ingredients         Weight Percent                                            ______________________________________                                        Dioctyl sebacate    0.05                                                      Benzyl alcohol      0.10                                                      Dow Corning 473 fluid                                                                             0.10                                                      (prepared by the Dow Corning                                                  Corporation)                                                                  TWEEN ® surfactant                                                                            0.03                                                      (prepared by ICI America                                                      Corporation)                                                                  One of the perfumery                                                                              0.10                                                      substances as set forth in                                                    Table II of Example V                                                         ______________________________________                                    

The perfuming substances as set forth in Table II of Example V add aromacharacteristics as set forth in Table II of Example V which are ratherintense and aesthetically pleasing to the users of the soft-feel,good-hold pump hair sprays.

EXAMPLE XII Conditioning Shampoos

Monamid CMA (prepared by the Mona Industries Company)(3.0 weightpercent) is melted with 2.0 weight percent coconut fatty acid (preparedby Procter & Gamble Company of Cincinnati, Ohio); 1.0 weight percentethylene glycol distearate (prepared by the Armak Corporation) andtriethanolamine (a product of Union Carbide Corporation)(1.4 weightpercent). The resulting melt is admixed with Stepanol WAT produced bythe Stepan Chemical Company (35.0 weight percent). The resulting mixtureis heated to 60° C. and mixed until a clear solution is obtained (at 60°C.).

GAFQUAT® polymer (manufactured by GAF Corporation of 140 West 51stStreet, New York, N.Y.)(5.0 weight percent) is admixed with 0.1 weightpercent sodium sulfite and 1.4 weight percent polyethylene glycol 6000distearate produced by Armak Corporation.

The resulting material is then mixed and cooled to 45° C. and 0.3 weightpercent of perfuming substance as set forth in Table II of Example V isadded to the mixture. The resulting mixture is cooled to 40° C. andblending is carried out for an additional one hour in each case. At theend of this blending period, the resulting material has a pleasantfragrance as indicated in Table II of Example V.

EXAMPLE XIII

Four drops of each of the substances set forth in Table II of Example V,supra, is added separately to two grams of AROMOX® DMC-W to produce aclear premix. The clear premix is added to 200 grams of CLOROX® withstirring resulting in a clear stable, single phase solution. sufficient1M aqueous NaOH is added to bring the pH of the mixture up to 12.8. Thesolution remains substantially stable at 120° F. for a period of sevendays. When the 5% aqueous sodium hypochlorite solution is used as alaundry bleach, the resulting laundry, on dry-out in an atmosphere of65% relative humidity yields substantially no characteristic"hypochlorite" odor, but does have a faint pleasant aroma as set forthin Table II of Example V. Furthermore, no such characteristic"hypochlorite" aroma is retained on the hands of the individual handlingsuch laundry in both the wet and the dry states.

EXAMPLE XIV

AROMOX® DMMC-W in various quantities is mixed with 0.1 grams of one ofthe substances set forth in Table II of Example V, supra. The resultingpremixes are then added to 200 grams of an aqueous 5% sodiumhypochlorite solution. Sufficient 12.5M aqueous NaOH is added to bringthe pH of the mixture up to 13. The following results are obtained:

    ______________________________________                                                           Clarity of Hypochlorite                                    Percentage AROMOX ®                                                                          solution after addition                                    DMMC-W             of premix                                                  ______________________________________                                        0.23%              Clear after three days                                     0.15%              Clear after three days                                     0.08%              Initially slightly turbid;                                                    two phases exist after                                                        three days.                                                ______________________________________                                    

When the 5% aqueous sodium hypochlorite solution is used as a laundrybleach, the resulting laundry on dry-out, in an atmosphere of 65%relative humidity, yields substantially no characteristic "hypochlorite"odor, but does have a faint, pleasant aroma as set forth in Table II ofExample V. Furthermore, no such characteristic "hypochlorite" aroma isretained on the hands of the individual handling such laundry in boththe wet and dry states.

What is claimed is:
 1. The process for preparing the compound having thestructure: ##STR113## comprising the steps of: (i) reacting the compoundhaving the structure: ##STR114## with a compound having the structure:##STR115## according to the reaction: ##STR116## (ii) then reacting thecompound thus formed having the structure: ##STR117## with baseaccording to the reaction: ##STR118## (iii) then reacting the thusformed compound having the structure: ##STR119## with a cupricsulfate-acetic anhydride mixture according to the reaction: ##STR120##(iv) then reacting the resulting product having the structure:##STR121## with methyl iodide in the presence of a lithiumdiisopropylamide catalyst having the structure: ##STR122## according tothe reaction: ##STR123## wherein X is an anion selected from the groupconsisting of: HSO₄ ⁻⁻ ;SO₄ ⁼ ; Cl⁻⁻ ; Br⁻⁻ ; PO₄.sup.═ ; H₂ PO₄ ⁻⁻ ;and HPO₄ ⁼ and M is an integer selected from the group consisting of 1,2 and 3.